Cationic aminoanthraquinones, their use for dyeing keratinous fibers, dyeing compositions containing them and methods of dyeing

ABSTRACT

Cationic aminoanthraquinones in which at least one cationic charge is delocalized on a 5-membered unsaturated polynitrogen-containing heterocycle, their use as a direct dye in dyeing compositions for keratinous materials, in particular for human keratinous fibers such as hair, dyeing compositions containing them, and dyeing methods using these compositions.

The present invention relates to aminoanthraquinones containing at leastone cationic group chosen from aliphatic chains containing at least onecationic charge delocalized on a 5-membered unsaturatedpolynitrogen-containing ring, their use as a direct dye in applicationsfor dyeing keratinous materials, such as human keratinous fibers, forexample hair, and dyeing compositions containing them.

It is known to dye keratinous fibers, and in particular hair, withdyeing compositions containing direct dyes. Direct dyes are dyemolecules having an affinity for keratinous fibers. The dyeing methodthat uses them is a so-called direct dyeing method which comprisesallowing the direct dyes to act on the fibers, and subsequently rinsingthe fibers.

The colors resulting therefrom are temporary or semipermanent colors,because the nature of the interactions which link the direct dyes to thekeratinous fiber, and their desorption from the surface and/or the coreof the fiber are responsible for their weak dyeing power and their poorresistance to washings and perspiration.

Cationic aminoanthraquinones whose charge is localized on the nitrogenatom have already been described among the known direct dyes. Suchaminoanthraquinones are described, for example, in French Patent No.1,422,016 and its addition No. 87,902, No. 1,391,675, No. 1,401,163, No.1,379,649, No. 1,430,089, No.1,584,965, No. 2,050,397, and No.2,548,895, U.S. Pat. Nos. 5,169,403, 5,314,505, 5,486,629, and5,520,707, and European Patent Nos. 818,193 and 852,136.

However, in hair dyeing, direct dyes are being continually sought whichexhibit increasingly better characteristics.

It is thus after major research studies carried out on this subject thatthe inventors have discovered new cationic aminoanthraquinones in whichat least one cationic charge is delocalized on a five-memberedunsaturated polynitrogen-containing heterocycle and contain at least onecationic group Z, Z being chosen from quaternized aliphatic chains,aliphatic chains containing at least one quaternized saturated ring, andaliphatic chains containing at least one quaternized unsaturated ring.

This new family of dyes can exhibit the very advantageous,characteristic feature of greater solubility in the dyeing media. Thesenew dyes can also generate colors, by direct dyeing, having an intensityand a resistance to various attacks to which the hair may be subjected:light, adverse weather conditions, shampoos, and perspiration, which issubstantially improved compared with that of the colors produced withknown prior art cationic aminoanthraquinones.

This discovery forms the basis of the present invention.

A subject of the present invention is thus aminoanthraquinones of theformula (I):

in which formula:

R₁, R₂, R₃ and R₄ which may be identical or different, are chosen from ahydrogen atom; a halogen atom; a group Z defined below; a (C₁-C₆)alkylradical; a monohydroxy(C₁-C₆ alkyl) radical; a polyhydroxy(C₂-C₆ alkyl)radical; a cyano radical; a nitro radical; a carboxyl radical; acarbamyl radical; a sulpho radical; an unsubstituted amino radical; asubstituted amino radical of formula NHR′₅, wherein R′₅ has the samemeaning as R₅ defined below, and wherein R′₅ may be identical to ordifferent from R₅; and an OR₆ and an SR₆ group, wherein R₆ is definedbelow;

R₅ is chosen from a hydrogen atom; a group Z defined below; a C₁-C₆alkyl radical; a monohydroxy(C₁-C₆alkyl) radical; a polyhydroxy(C₂-C₆alkyl) radical; a (C₁-C₆)alkoxy(C₁-C₆ alkyl) radical; an aryl radical; abenzyl radical; a cyano(C₁-C₆ alkyl) radical; a carbamyl(C₁-C₆ alkyl)radical; an N-(C₁-C₈)alkylcarbamyl(C₁-C₆ alkyl) radical; anN,N-di(C₁-C₆)alkylcarbamyl(C₁-C₆ alkyl) radical; a thiocarbamyl(C₁-C₆alkyl) radical; a trifluoro(C₁-C₆ alkyl) radical; a sulpho(C₁-C₆ alkyl)radical; a (C₁-C₆)alkylcarboxy(C₁-C₆ alkyl) radical; a(C₁-C₆)alkylsulphinyl(C₁-C₆ alkyl) radical; an aminosulphonyl(C₁-C₆alkyl) radical; an N-Z-aminosulphonyl(C₁-C₆ alkyl) radical; anN-(C₁-C₆)alkylaminosulphonyl(C₁-C₆ alkyl) radical; anN,N-di(C₁-C₆)alkylaminosulphonyl(C₁-C₆ alkyl) radical; a(C₁-C₆)alkylcarbonyl(C₁-C₆ alkyl) radical; an amino(C₁-C₆ alkyl)radical, wherein the alkyl portion is unsubstituted or substituted withat least one hydroxyl radical; an amino(C₁-C₆ alkyl) radical, whereinthe alkyl is substituted with at least one hydroxyl radical and whereinthe amine is substituted with one or two radicals, wherein each amineradical is identical or different, and is chosen from C₁-C₆ alkyl,monohydroxy(C₁-C₆ alkyl), polyhydroxy(C₂-C₆ alkyl),(C₁-C₆)alkylcarbonyl, carbamyl, N-(C₁-C₆)alkylcarbamyl,N,N-di(C₁-C₆)-alkylcarbamyl, (C₁-C₆)alkylsulphonyl, formyl,trifluoro(C₁-C₆)alkylcarbonyl, (C₁-C₆)alkylcarboxyl, thiocarbamyl, andthe group Z defined below, or may form, together with the nitrogen atomto which they are attached, a 5- or 6-membered ring containing carbon orcontaining at least one heteroatom;

R₆ is chosen from a hydrogen atom; a C₁-C₆ alkyl radical; amonohydroxy(C₁-C₆ alkyl) radical; a polyhydroxy(C₂-C₆ alkyl) radical; agroup Z defined below; a (C₁-C₆)alkoxy(C₁-C₆ alkyl) radical; an arylradical; a benzyl radical; a carboxy(C₁-C₆ alkyl) radical; a(C₁-C₆)alkylcarboxy(C₁-C₆ alkyl) radical; a cyano(C₁-C₆ alkyl) radical;a carbamyl(C₁-C₆ alkyl) radical; an N-(C₁-C₆)alkylcarbamyl(C₁-C₆ alkyl)radical; an N,N-di(C₁-C₆)alkylcarbamyl(C₁-C₆ alkyl) radical; atrifluoro(C₁-C₆ alkyl) radical; an aminosulphonyl(C₁-C₆ alkyl) radical;an N-Z-aminosulphonyl(C₁-C₆ alkyl) radical; anN-(C₁-C₆)alkylaminosulphonyl(C₁-C₆ alkyl) radical; anN,N-di(C₁-C₆)alkylaminosulphonyl(C₁-C₆ alkyl) radical; a(C₁-C₆)alkylsulphinyl(C₁-C₆ alkyl) radical; a(C₁-C₆)alkylsulphonyl(C₁-C₆ alkyl) radical; a (C₁-C₆)alkylcarbonyl(C₁-C₆alkyl) radical; an amino(C₁-C₆ alkyl) radical, wherein the alkyl isunsubstituted or substituted with at least one hydroxyl radical; anamino(C₁-C₆ alkyl) radical, wherein the alkyl is substituted with atleast one hydroxyl radical and wherein the amine is substituted with oneor two radicals, which radicals are identical or different, and arechosen from C₁-C₆ alkyl, monohydroxy(C₁-C₆ alkyl), polyhydroxy(C₂-C₆alkyl), (C₁-C₆)alkylcarbonyl, formyl, trifluoro(C₁-C₆)alkylcarbonyl,(C₁-C₆)alkylcarboxyl, carbamyl, N-(C₁-C₆)alkylcarbamyl,N,N-di(C₁-C₆)alkylcarbamyl, thiocarbamyl, and (C₁-C₆)alkylsulphonylradicals, and from the group Z defined below, or which may form,together with the nitrogen atom to which they are attached, a 5- or6-membered ring containing carbon or containing at least one heteroatom;

Z is chosen from the unsaturated cationic groups of formulae (II) and(III), and the saturated cationic groups of formula (IV):

 in which:

D is a linking arm chosen from linear and branched alkyl chains, whichmay be interrupted by at least one heteroatom such as oxygen, sulphur ornitrogen, and which may be substituted with at least one radical chosenfrom hydroxyl and C₁-C₆ alkoxy, and which may carry at least one ketonefunction; in one embodiment of the invention, the alkyl chains containfrom 1 to 14 carbon atoms;

the members E, G, J, L and M, which are identical or different, arechosen from carbon, oxygen, sulphur and nitrogen atoms;

n is an integer ranging from 0 to 4;

m is an integer ranging from 0 to 5;

the radicals R, which are identical or different, are chosen from agroup Z′, which has the same definition as the group Z, and whichdefinition is identical to or different from the group Z; a halogenatom; a hydroxyl radical; a C₁-C₆ alkyl radical; a monohydroxy(C₁-C₆alkyl) radical; a polyhydroxy(C₂-C₆ alkyl) radical; a nitro radical; acyano radical; a cyano(C₁-C₆ alkyl) radical; a C₁-C₆ alkoxy radical; atri(C₁-C₆)alkylsilane(C₁-C₆ alkyl) radical; an amido radical; analdehydo radical; a carboxyl radical; a C₁-C₆ alkylcarbonyl radical; athio radical; a thio(C₁-C₆ alkyl) radical; a (C₁-C₆)alkylthio radical;an amino radical; an amino radical protected with a radical chosen from(C₁-C₆)alkylcarbonyl, carbamyl, and (C₁-C₆)alkylsulphonyl; a group NHR″and a group NR″R′″, wherein R″ and R′″, which are identical ordifferent, are chosen from a C₁-C₆ alkyl radical, a monohydroxy(C₁-C₆alkyl) radical, and a polyhydroxy(C₂-C₆ alkyl) radical;

R₇ is chosen from a C₁-C₆ alkyl radical, a monohydroxy(C₁-C₆ alkyl)radical, a polyhydroxy(C₂-C₆ alkyl) radical, a cyano(C₁-C₆ alkyl)radical, a tri(C₁-C₆)alkylsilane(C₁-C₆ alkyl) radical, a(C₁-C₆)alkoxy(C₁-C₆ alkyl) radical, a carbamyl(C₁-C₆ alkyl) radical, a(C₁-C₆)alkylcarboxy(C₁-C₆ alkyl) radical, a benzyl radical, and a groupZ′, having the same definition as the group Z, and which definition isidentical to or different from the group Z;

R₈, R₉ and R₁₀, which are identical or different, are chosen from aC₁-C₆ alkyl radical; a monohydroxy(C₁-C₆ alkyl) radical; apolyhydroxy(C₂-C₆ alkyl) radical; a (C₁-C₆)alkoxy(C₁-C₆ alkyl) radical;a cyano(C₁-C₆ alkyl) radical; an aryl radical; a benzyl radical; anamido(C₁-C₆ alkyl) radical; a tri(C₁-C₆)alkylsilane(C₁-C₆ alkyl)radical; and an amino(C₁-C₆ alkyl) radical, wherein the amine isprotected with a radical chosen from (C₁-C₆)alkylcarbonyl, carbamyl, and(C₁-C₆)alkylsulphonyl; two of the radicals R₈, R₉ and R₁₀ may also form,together with the nitrogen atom to which they are attached, a saturated5- or 6-membered ring containing carbon or capable of containing atleast one heteroatom such as, for example, a pyrrolidine ring, apiperidine ring, a piperazine ring or a morpholine ring, it beingpossible for the ring to be unsubstituted or substituted with asubstituent chosen from a halogen atom, a hydroxyl radical, a C₁-C₆alkyl radical, a monohydroxy(C₁-C₆ alkyl) radical, a polyhydroxy(C₂-C₆alkyl) radical, a nitro radical, a cyano radical, a cyano(C₁-C₆ alkyl)radical, a C₁-C₆ alkoxy radical, a tri(C₁-C₆)alkylsilane(C₁-C₆ alkyl)radical, an amido radical, an aldehydo radical, a carboxyl radical, aketo(C₁-C₆ alkyl) radical, a thio radical, a thio(C₁-C₆ alkyl) radical,a (C₁-C₆)alkylthio radical, an amino radical, or an amino radicalprotected with a radical chosen from (C₁-C₆)alkylcarbonyl, carbamyl, and(C₁-C₆)alkylsulphonyl; one of the radicals R₈, R₉ and R₁₀ may also bechosen from the group Z′, having the same definition as the group Z, andwhich definition is identical or different from the group Z;

R₁₁ is chosen from a C₁-C₆ alkyl radical; a monohydroxy(C₁-C₆ alkyl)radical; a polyhydroxy(C₂-C₆ alkyl) radical; an aryl radical; a benzylradical; an amino(C₁-C₆ alkyl) radical, an amino(C₁-C₆ alkyl) radical,wherein the amine is protected with a radical chosen from a(C₁-C₆)alkylcarbonyl, a carbamyl, and a (C₁-C₆)alkylsulphonyl; acarboxy(C₁-C₆ alkyl) radical; a cyano(C₁-C₆ alkyl) radical; acarbamyl(C₁-C₆ alkyl) radical; a trifluoro(C₁-C₆ alkyl) radical; atri(C₁-C₆)alkylsilane(C₁-C₆ alkyl) radical; a sulphonamido(C₁-C₆ alkyl)radical; a (C₁-C₆)alkylcarboxy(C₁-C₆ alkyl) radical; a(C₁-C₆)alkylsulphinyl(C₁-C₆ alkyl) radical; a(C₁-C₆)alkylsulphonyl(C₁-C₆ alkyl) radical; a (C₁-C₆)alkylketo(C₁-C₆alkyl) radical; an N-(C₁-C₆)alkylcarbamyl(C₁-C₆ alkyl) radical; and anN-(C₁-C₆)alkylsulphonamido(C₁-C₆ alkyl) radical;

x and y are the integers 0 or 1, with the following conditions:

in the unsaturated cationic groups of formula (II):

when x is 0, the linking arm D is attached to the nitrogen atom;

when x is 1, the linking arm D is attached to one of the members E, G, Jor L;

y is 1:

1) when the members E, G, J and L are simultaneously a carbon atom, andR₇ is carried by the nitrogen atom of the unsaturated ring; or

2) when at least one of the members E, G, J and L is a nitrogen atomonto which the radical R₇ is attached;

in the unsaturated cationic groups of formula (III):

when x is 0, the linking arm D is attached to the nitrogen atom;

when x is 1, the linking arm D is attached to one of the members E, G,J, L or M;

y is 1 when at least one of the members E, G, J, L and M is a divalentatom, and R₇ is carried by the nitrogen atom of the unsaturated ring;

in the cationic groups of formula (IV):

if x is 0, then the linking arm D is attached to the nitrogen atomcarrying the radicals R₈ to R₁₀;

if x is 1, then two of the radicals R₈ to R₁₀ conjointly form, with thenitrogen atom to which they are attached, a saturated 5- or 6-memberedring as defined above; and the linking arm D is carried by a carbon atomof the said saturated ring;

X⁻ is chosen from monovalent and divalent anions; in one embodiment ofthe invention, X⁻ is chosen from: (i) a halogen atom such as chlorine,bromine, fluorine, and iodine, (ii) a hydroxide, (iii) a hydrogensulphate, and (iv) a (C₁-C₆)alkylsulphate such as, for example, methylsulphates and ethyl sulphates;

it being understood that the number of unsaturated cationic groups Z offormula (II), in which at least one of the members E, G, J and L is anitrogen atom, is at least equal to 1.

The compounds of formula (I) may be optionally salified with stronginorganic acids such as HCl, HBr, and H₂SO₄, or organic acids such asacetic, lactic, tartaric, citric, and succinic acids.

The alkyl and alkoxy radicals cited above in the formulae (I), (II),(III) and (IV) may be linear or branched.

Examples of rings of the unsaturated groups Z of formula (II) above,include the pyrrole, imidazole, pyrazole, oxazole, thiazole, andtriazole rings.

The rings of the unsaturated groups Z of formula (III), above, may be,for example, pyridine, pyrimidine, pyrazine, oxazine, and triazinerings.

In one embodiment of the invention, the compounds of formula (I) arechosen from:

1-[2-(9,10-Dioxo-9,10-dihydroanthracen-1-ylamino)ethyl]-3-methyl-3H-imidazol-1-iumbromide,

1-Methyl-3-[3-(4-methylamino-9,10-dioxo-9,10-dihydroanthracen-1-ylamino)propyl]-3H-imidazol-1-iumhydrogen sulphate,

1-[2-(4-Hydroxy-9,10-dioxo-9,10-dihydroanthracen-1-ylamino)ethyl]-3-methyl-3H-imidazol-1-iumbromide,

1-[3-(9,10-Dioxo-9,10-dihydroanthracen-1-ylamino)propyl]-3-methyl-3H-imidazol-1-iummethosulphate,

1-[3-(4-Hydroxy-9,10-dioxo-9,10-dihydroanthracen-1-ylamino)propyl]-3-methyl-3H-imidazol-1-iummethosulphate,

1-{3-[4-(2-Hydroxyethylamino)-9,10-dioxo-9,10-dihydroanthracen-1-ylamino]propyl}-3-methyl-3H-imidazol-1-iummethosulphate,

1-{3-[4-(2,3-Dihydroxypropylamino)-9,10-dioxo-9,10-dihydroanthracen-1-ylamino]propyl}-3-methyl-3H-imidazol-1-iummethosulphate,

1,4-bis[3-(9,10-Dioxo-9,10-dihydroanthracen-1,4-diylamino)propyl]-3-methyl-3H-imidazol-1-iumdimethosulphate,

1-[2-(9,10-Dioxo-9,10-dihydroanthracen-2-ylamino)ethyl]-3-methyl-3H-imidazol-1-iumbromide,

1-[2-(9,10-Dioxo-9,10-dihydroanthracen-2-ylamino)ethyl]-2-methyl-3H-pyrazol-1-iumbromide,

1-[2-(9,10-Dioxo-9,10-dihydroanthracen-1-ylamino)ethyl]-2-methyl-3H-pyrazol-1-iumbromide,

1,5-bis[3-(9,10-Dioxo-9,10-dihydroanthracen-1,5-diylamino)propyl]-3-methyl-3H-imidazol-1-iumdimethosulphate,

1,8-bis[3-(9,10-Dioxo-9,10-dihydroanthracen-1,8-diylamino)propyl]-3-methyl-3H-imidazol-1-iumdimethosulphate,

1-[2-(5,8-Diamino-9,10-dioxo-9,10-dihydroanthracen-1-ylamino)ethyl]-3-methyl-3H-imidazol-1-iumbromide, and

1-[3-(5,8-Diamino-9,10-dioxo-9,10-dihydroanthracen-1-ylamino)propyl]-3-methyl-3H-imidazol-1-iummethosulphate.

The compounds of formula (I) in accordance with the invention may beeasily obtained, according to methods well known in the state of the artfor the production of quaternized amines, for example:

in a single step, by condensation of an anthraquinone containing ahaloalkyl radical with a compound carrying a tertiary amine radical, orby condensation of an anthraquinone containing a tertiary amine radicalwith a compound carrying a haloalkyl radical; or

in two steps, by condensation of an anthraquinone containing a haloalkylradical with a compound carrying a secondary amine, or by condensationof a halogenated or hydroxylated anthraquinone with anamino(disubstituted)alkylamine, followed by quaternization with analkylating agent.

The quaternization step is generally, for the sake of convenience, thelast step in the synthesis, but may occur earlier in the sequence ofreactions leading to the preparation of the compounds of formula (I).

A subject of the invention is also dyeing compositions for keratinousmaterials, comprising, in a medium appropriate for dyeing, an effectivequantity for dyeing keratinous materials of at least one cationicaminoanthraquinone of formula (I) defined above.

Another subject of the invention is direct dyeing compositions for humankeratinous fibers, and in particular hair, comprising, in a mediumappropriate for dyeing, an effective quantity for dyeing keratinousmaterials of at least one cationic aminoanthraquinone as defined aboveby formula (I).

Another subject of the invention is the use of the cationicaminoanthraquinones of formula (I), as direct dyes, in, or for thepreparation of, dyeing compositions for keratinous materials, inparticular for human keratinous fibers such as hair.

However other characteristics, aspects and advantages of the inventionwill emerge even more clearly on reading the description which follows,as well as the various concrete, but not at all limiting, examplesintended to illustrate it.

In one embodiment of the dyeing composition in accordance with theinvention, the amount of the at least one cationic aminoanthraquinone offormula (I) in the dyeing composition ranges from about 0.005 to about12%, relative to the total weight of the dyeing composition. In anotherembodiment, the amount of the at least one cationic aminoanthraquinoneranges from about 0.05 to about 6% by weight, relative to the totalweight of the composition.

In order to obtain a variety of colors, the dyeing composition accordingto the invention may also contain, in addition to the cationicaminoanthraquinones of formula (I), at least one additional direct dyethat is conventionally used in the art. Examples of the at least oneadditional direct dye include:

nitrobenzene dyes, such as nitrophenylenediamines, nitrodiphenylamines,nitroanilines, nitrophenol ethers, nitrophenols, and nitropyridines;

anthraquinone dyes other than those of formula (I);

mono- and diazo, triarylmethane, azine, acridine and xanthene dyes; and

metal-containing dyes.

The total amount of all these other direct addition dyes in the dyecomposition according to the present invention may range from about 0.05to about 10% by weight relative to the total weight of the dyeingcomposition.

The cationic aminoanthraquinones of formula (I) may also be incorporatedinto dyeing compositions for oxidation dyeing which contains oxidationbases and optionally couplers, to increase the shimmer of the shadesobtained with the oxidation dyes.

The medium (or carrier) appropriate for dyeing is generally water or amixture of water and at least one organic solvent for solubilizing thecompounds which would not be sufficiently soluble in water. Examples oforganic solvents include lower C₁-C₄ alkanols, such as ethanol andisopropanol; glycerol; glycols and glycol ethers, such as2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether;aromatic alcohols, such as benzyl alcohol or phenoxyethanol; and similarproducts and mixtures thereof.

In one embodiment of the invention, the solvents may be present in anamount ranging from approximately 1 to approximately 40% by weightrelative to the total weight of the dyeing composition. In anotherembodiment of the invention, the amount of solvents ranges fromapproximately 5 to approximately 30% by weight, relative to the weightof the composition.

It is also possible to add to the composition according to the inventionfatty amides such as mono- and diethanolamides of acids derived fromcopra, lauric acid and oleic acid, in amounts ranging from about 0.05 toabout 10% by weight, relative to the weight of the composition.

It is also possible to add to the composition according to the inventionwell-known state of the art surfactants of the anionic, cationic,nonionic, amphoteric or zwitterionic type or mixtures thereof. In oneembodiment of the invention, these surfactants can be present in thecomposition in an amount ranging from about 0.1 to about 50% by weight,relative to the total weight of the composition. In another embodimentof the invention, the amount of these surfactants ranges from about 1 toabout 20% by weight, relative to the total weight of the composition.

It is also possible to use thickening agents in an amount ranging fromabout 0.2 to about 5% by weight, relative to the total weight of thecomposition.

The dyeing composition according to the invention may contain, inaddition, various customary adjuvants, such as antioxidants, perfumes,sequestering agents, dispersing agents, hair conditioners,preservatives, and opacifying agents, as well as any other adjuvantnormally used in dyeing keratinous materials.

Of course persons skilled in the art will be careful to choose theoptional additional compounds mentioned above such that the advantageousproperties intrinsically attached to the dyeing composition according tothe invention are not, or not substantially adversely modified by theaddition(s) envisaged.

The dyeing composition according to the invention may be formulated atacidic, neutral or alkaline pH, it being possible for the pH to vary,for example, from approximately 3 to approximately 12. In one embodimentof the invention, the pH varies from approximately 5 to approximately11. The pH can be adjusted by means of previously well-knownalkalinizing agents or acidifying agents or buffers.

Suitable alkalinizing agents include ammonium hydroxide, alkali metalcarbonates, alkanolamines such as mono-, di- and triethanolamines aswell as their derivatives, sodium and potassium hydroxides and thecompounds of formula:

in which W is a propylene residue optionally substituted with a groupchosen from a hydroxyl group and a C₁-C₄ alkyl radical; R₁₂, R₁₃, R₁₄and R₁₅, simultaneously or independently of each other, are chosen froma hydrogen atom, a C₁-C₆ alkyl radical, and a hydroxy(C₁-C₆ alkyl)radical.

The acidifying agents are conventionally inorganic or organic acids suchas, for example, hydrochloric, tartaric, citric and phosphoric acids. Anexample of a buffer is potassium dihydrogen phosphate/sodium hydroxide.

The composition applied to the hair may be provided in various forms,such as in liquid, cream or gel form, or in any other form appropriatefor dyeing keratinous fibers. In particular, it can be packaged underpressure in an aerosol can in the presence of a propellant and can forma foam.

Another subject of the present invention relates to a method of dyeingkeratinous fibers, in particular human keratinous fibers such as hair,by direct dyeing, comprising allowing a dyeing composition containing atleast one cationic aminoanthraquinone of formula (I) to act on dry orwet keratinous fibers. It is possible to use the composition accordingto the invention as a leave-in composition, that is to say that afterapplying the composition to the fibers, they are dried withoutintermediate rinsing.

In one embodiment, the process comprises allowing the composition to acton the fibers for an exposure time ranging from 3 to 60 minutesapproximately, rinsing the fibers, optionally washing the fibers, andrinsing the fibers again and drying the fibers. In another embodiment ofthe invention, the process is similar to that just described, exceptthat the exposure time ranges 5 to 45 minutes approximately.

Concrete and nonlimiting examples illustrating the invention will now begiven.

EXAMPLES OF PREPARATION Example 1 Preparation of1-[2-(9,10-dioxo-9,10dihydroanthracen-1-ylamino)ethyl]-3-methyl-3H-imidazol-1-iumbromide, (Charge Delocalized in the Imidazole Ring)

16.5 g (0.05 mol) of 1-(2-bromoethylamino)anthraquinone (RN-3591-05-7)and 4.9 g (0.06 mol) of 1-methyl-1H-imidazole (RN-616-47-7) weresuspended in 50 ml of toluene.

The mixture was then heated, with stirring, at the reflux temperature oftoluene, for 4 hours (which corresponded with the disappearance of thestarting anthraquinone in thin-layer chromatography) and then theboiling product was dewatered and it was washed twice in ethyl acetate.

After drying at 40° C. under vacuum, red crystals (19.2 g) wereobtained, which melted with decomposition at 184-186° C. (Kofler).

The elemental analysis for C₂₀H₁₈N₃O₂Br was:

% C H N 0 Br theory 58.27 4.40 10.19 7.79 19.38 found 58.26 4.42 10.047.85 19.26

Example 2 Preparation of1-methyl-3-[3-(4-methylamino-9,10-dioxo-9,10dihydroanthracen-1-ylamino)propyl]-3H-imidazol-1-iumhydrogen sulphate, (Charge Delocalized in the Imidazole Ring)

In a first step, 1-(3-imidazolylpropylamino)-4-methylaminoanthraquinonewas prepared by heating for 9 hours on a boiling waterbath and withstirring, the mixture comprising 47.4 g (0.15 mol) of1-bromo-4-methylaminoanthraquinone (RN 128-93-8), 56.3 g (0.45 mol) of3-imidazol-1-ylpropylamine (RN 5036-48-6) and 3.0 g of copper sulphatepentahydrate, in 60 ml of 1-methyl-2-pyrrolidone.

The mixture was then poured over 300 g of ice-cold water, thecrystallized precipitate thus obtained was dewatered, the precipitatewas made into a paste again in water and dried at 40° C. under vacuumover phosphoric anhydride.

45.1 g of dark blue crystals were obtained which, after purification byrecrystallization from boiling 1,2-dimethoxyethane, melted at 140° C.(Kofler). The elemental analysis for C₂₁H₂₀N₄O₂ was:

% C H N O theory 69.98 5.59 15.54 8.88 found 69.85 5.64 15.60 8.99

In a second step, and in order to quaternize the1-(3-imidazolylpropylamino)-4-methylaminoanthraquinone obtained in thefirst step, 4.7 g (0.013 mol) of1-(3-imidazolylpropylamino)-4-methylaminoanthraquinone and 1.37 ml(0.0143 mol) of dimethyl sulphate were suspended in 25 ml ofchlorobenzene and the mixture was heated, with stirring, for 3 hours at45° C.

The blue oil in suspension obtained was separated after settling out andwashed several times in ethyl acetate and then dried under vacuum at 50°C.

3.8 g of a dark blue compound were obtained, which compound crystallizedafter purification and whose melting point (Kofler) was 192-194° C. Thestructure was in conformity in ¹H and ¹³C NMR.

Examples of Dyeing Compositions Example 3

The following dyeing composition was prepared:

Aminoanthraquinone prepared in Example 1 (10⁻³ mol) 0.412 g Benzylalcohol 4.0 g Polyethylene glycol 6EO 6.0 g Hydroxyethylcellulose 0.7 gAlkylpolyglucoside in aqueous solution containing 4.5 g A.M. 60% A.M.*Phosphate buffer qs pH 7 Demineralized water qs 100 g *Active material

The above composition was applied to locks of permanently waved ornatural grey hair which was 90% white and allowed to act for 20 minutes.After rinsing with running water and drying, the hair was dyed in acopper-colored red shade.

Example 4

The following dyeing composition was prepared:

Aminoanthraquinone prepared in Example 2 0.49 g Oleic diethanolamide 3 gLauric acid 1 g Ethylene glycol monoethyl ether 5 gHydroxyethylcellulose 2 g 2-Amino-2-methyl-1-propanol qs pH 9.5Demineralized water qs 100 g

The above composition was applied to locks of permanently waved ornatural grey hair which was 90% white and allowed to act for 30 minutes.After rinsing with running water and drying, the hair was dyed anintense blue shade.

Comparative Example 5 and 6

In parallel with the composition of Example 3, two comparativecompositions (3A) and (3B) were prepared which, as a replacement for thecationic aminoanthraquinone of the invention contained, in molarequivalent, two cationic aminoanthraquinones of the prior art describedin French Patent No. 1,379,649, and in which the cationic charge waslocated on the nitrogen:

Comparative Composition (3A)

with:

Comparative Composition (3B)

with

The other constituents of comparative compositions (3A) and (3B) wereidentical, in type and concentration, to those of composition 3 inaccordance with the invention.

Locks of hair were then dyed with each of the comparative compositions(3A) and (3B) according to the same protocol and with the same hairquality as in Example 3.

The shades obtained with the aid of each of the three compositions andthe shade of the non-dyed hair (control composition) were measured witha Minolta CM 2002 colorimeter and expressed as H, V, C, in the MUNSELLnotation (ASTM D 1535-68 standard), H designating the shade or HUE, Vdesignating the intensity or VALUE, and C the purity or CHROMATICITY.

These values, on the basis of permanently dyed hair, are presented inthe following Table (I):

TABLE (I) COMPOSITION S H V C (3) 7.5R 3.8 6.3 (3A) 8.6R 3.7 6.3 (3B)8.8R 4.1 6.7 Control 4.0Y 5.4 1.4

The locks dyed with the aid of each of the three compositions 3, (3A)and (3B) were then subjected to a light test (XENOTEST).

Description of the Test of Resistance to Light (Xenotest)

The dyed hairs are attached to a support (cardboard or plastic). Thesesupports are placed on sample holders which rotate around a Xenon lampfor a period of 40 hours at a humidity level of 60% RH (RelativeHumidity) and at a temperature of 25° C.

The shades of the locks which were subjected to a light test were thenmeasured using the CM 2002 colorimeter and exhibited the following[combined in Table (11) below]:

TABLE (II) COMPOSITION S H V C (3) 9.1R 3.9 5.9 (3A) 0.8YR 4.1 5.5 (3B)0.8YR 4.2 5.6

The variation in color between the locks dyed before Xenotest and thosedyed after Xenotest was quantified using the NICKERSON equation whichdefines the color variation indices: I=(C/5)×2ΔH+6ΔV+3ΔC (this equationbeing described in the publication: “Journal of the Optical Society ofAmerica”, 1944-Sept-Vol34-No.9-p550-570), and the percentagedeterioration of the shades, caused by the light test, was evaluatedbased on the equation I_(b)/I_(a)×100, I_(b) defining the colorvariation index between the locks dyed after Xenotest and the locks dyedbefore Xenotest, I_(a) defining the color variation index between thelocks dyed before Xenotest and the control locks.

Thus, for each of the three shades obtained with the compositions 3,(3A) and (3B), the percentages of deterioration were the following:

with composition 3 17.4% with composition (3A) 30.9% with composition(3B)  28.8%.

Conclusion

The composition for direct dyeing comprising an aminoanthraquinoneaccording to the present invention (composition 3) produced a shadewhich was more resistant to light than those obtained with the twocompositions for direct dyeing comprising prior art aminoanthraquinones[compositions (3A) and (3B)]: only 17.4% of deterioration for thecomposition according to the present invention, compared with 30.9% and28.8%, respectively for the two prior art compositions.

What is claimed is:
 1. A cationic aminoanthraquinone of formula (I) oran acid-addition salt thereof:

in which: R₁, R₂, R₃ and R₄, which may be identical or different, arechosen from a hydrogen atom; a halogen atom; a group Z defined below; a(C₁-C₆)alkyl radical; a monohydroxy(C₁-C₆ alkyl) radical; apolyhydroxy(C₂-C₆ alkyl) radical; a cyano radical; a nitro radical; acarboxyl radical; a carbamyl radical; a sulpho radical; an unsubstitutedamino radical; a substituted amino radical NHR′₅, wherein R′₅ has thesame definition as R₅ below, and wherein R′₅ may be identical to ordifferent from R₅ below; and an OR₆ and SR₆ group, wherein R₆ is asdefined below; R₅ is chosen from a hydrogen atom; a group Z definedbelow; a C₁-C₆ alkyl radical; a monohydroxy(C₁-C₆ alkyl) radical; apolyhydroxy(C₂-C₆ alkyl) radical; a (C₁-C₆)alkoxy(C₁-C₆ alkyl) radical;an aryl radical; a benzyl radical; a cyano(C₁-C₆ alkyl) radical; acarbamyl(C₁-C₆ alkyl) radical; an N-(C₁-C₆)alkylcarbamyl(C₁-C₆ alkyl)radical; an N,N-di(C₁-C₆)alkylcarbamyl(C₁-C₆ alkyl) radical; athiocarbamyl(C₁-C₆ alkyl) radical; a trifluoro(C₁-C₆ alkyl) radical; asulpho(C₁-C₆ alkyl) radical; a (C₁-C₆)alkylcarboxy(C₁-C₆ alkyl) radical;a (C₁-C₆)alkylsulphinyl(C₁-C₆ alkyl) radical; an aminosulphonyl(C₁-C₆alkyl) radical; an N-Z-aminosulphonyl(C₁-C₆ alkyl) radical; anN-(C₁-C₆)alkylaminosulphonyl(C₁-C₆ alkyl) radical; anN,N-di(C₁-C₆)alkylaminosulphonyl(C₁-C₆ alkyl) radical; a(C₁-C₆)alkylcarbonyl(C₁-C₆ alkyl) radical; an amino(C₁-C₆ alkyl)radical, wherein the alkyl is unsubstituted or substituted with at leastone hydroxyl radical; an amino(C₁-C₆ alkyl) radical, wherein the alkylis substituted with at least one hydroxyl radical and wherein the amineis substituted with one or two radicals, which are identical ordifferent, and which are chosen from C₁-C₆ alkyl, monohydroxy(C₁-C₆alkyl), polyhydroxy(C₂-C₆ alkyl), (C₁-C₆)alkylcarbonyl, carbamyl,N-(C₁-C₆)alkylcarbamyl, N,N-di(C₁-C₆)alkylcarbamyl,(C₁-C₆)alkylsulphonyl, formyl, trifluoro(C₁-C₆)alkylcarbonyl,(C₁-C₆)alkylcarboxyl, thiocarbamyl, and a group Z defined below, orwhich may form, together with the nitrogen atom to which they areattached, a 5- or 6-membered ring containing atoms chosen from carbonand heteroatoms; R₆ is chosen from a hydrogen atom; a C₁-C₆ alkylradical; a monohydroxy(C₁-C₆ alkyl) radical; a polyhydroxy(C₂-C₆ alkyl)radical; a group Z defined below; a (C₁-C₆)alkoxy(C₁-C₆ alkyl) radical;an aryl radical; a benzyl radical; a carboxy(C₁-C₆ alkyl) radical; a(C₁-C₆)alkylcarboxy(C₁-C₆ alkyl) radical; a cyano(C₁-C₆ alkyl) radical;a carbamyl(C₁-C₆ alkyl) radical; an N-(C₁-C₆)alkylcarbamyl(C₁-C₆ alkyl)radical; an N,N-di(C₁-C₆)alkylcarbamyl(C₁-C₆ alkyl) radical; atrifluoro(C₁-C₆ alkyl) radical; an aminosulphonyl(C₁-C₆ alkyl) radical;an N-Z-aminosulphonyl(C₁-C₆ alkyl) radical; anN-(C₁-C₆)alkylaminosulphonyl(C₁-C₆ alkyl) radical; anN,N-di(C₁-C₆)alkylaminosulphonyl(C₁-C₆ alkyl) radical; a(C₁-C₆)alkylsulphinyl(C₁-C₆ alkyl) radical; a(C₁-C₆)alkylsulphonyl(C₁-C₆ alkyl) radical; a (C₁-C₆)alkylcarbonyl(C₁-C₆alkyl) radical; an amino(C₁-C₆ alkyl) radical, wherein the alkyl isunsubstituted or substituted with at least one hydroxyl radical; anamino(C₁-C₆ alkyl) radical, wherein the alkyl is substituted with atleast one hydroxyl radical and wherein the amine is substituted with oneor two radicals, which are identical or different, and which are chosenfrom C₁-C₆ alkyl, monohydroxy(C₁-C₆ alkyl), polyhydroxy(C₂-C₆ alkyl),(C₁-C₆)alkylcarbonyl, formyl, trifluoro(C₁-C₆)alkylcarbonyl,(C₁-C₆)alkylcarboxyl, carbamyl, N-(C₁-C₆)alkylcarbamyl,N,N-di(C₁-C₆)alkylcarbamyl, thiocarbamyl, and (C₁-C₆)alkylsulphonylradicals, and from a group Z defined below, or which may form, togetherwith the nitrogen atom to which they are attached, a 5- or 6-memberedring containing atoms chosen from carbon and heteroatoms; Z is chosenfrom the unsaturated cationic groups of formulae (II) and (III ), andthe saturated cationic groups of formula (IV):

 in which: D is a linking arm which is chosen from linear and branchedalkyl chains, which may be interrupted by at least one heteroatom, andwhich may be substituted with at least one radical chosen from ahydroxyl and a C₁-C₆ alkoxy, and which may carry at least one ketonefunction; E, G, J, L and M, which are identical or different, are chosenfrom carbon, oxygen, sulphur, and nitrogen atoms; n is an integerranging from 0 to 4; m is an integer ranging from 0 to 5; the radicalsR, which are identical or different, are chosen from a group Z′, whereinZ′ has the same definition as Z, and wherein the group Z′ is identicalor different from the group Z; a halogen atom; a hydroxyl radical; aC₁-C₆ alkyl radical; a monohydroxy(C₁-C₆ alkyl) radical; apolyhydroxy(C₂-C₆ alkyl) radical; a nitro radical; a cyano radical; acyano(C₁-C₆ alkyl) radical; a C₁-C₆ alkoxy radical; atri(C₁-C₆)alkylsilane(C₁-C₆ alkyl) radical; an amido radical; analdehydo radical; a carboxyl radical; a C₁-C₆ alkylcarbonyl radical; athio radical; a thio(C₁-C₆ alkyl) radical; a (C₁-C₆)alkylthio radical;an amino radical; an amino radical protected with a radical chosen from(C₁-C₆)alkylcarbonyl, carbamyl, and (C₁-C₆)alkylsulphonyl; and an NHR″and an NR″R′″ group, wherein R″ and R′″, which are identical ordifferent, are chosen from a C₁-C₆ alkyl radical, a monohydroxy(C₁-C₆alkyl) radical, and a polyhydroxy(C₂-C₆ alkyl) radical; R₇ is chosenfrom a C₁-C₆ alkyl radical; a monohydroxy(C₁-C₆ alkyl) radical; apolyhydroxy(C₂-C₆ alkyl) radical; a cyano(C₁-C₆ alkyl) radical; atri(C₁-C₆)alkylsilane(C₁-C₆ alkyl) radical; a (C₁-C₆)alkoxy(C₁-C₆ alkyl)radical; a carbamyl(C₁-C₆ alkyl) radical; a (C₁-C₆)alkylcarboxy(C₁-C₆alkyl) radical; a benzyl radical; and a group Z′, wherein Z′ has thesame definition as Z, and wherein the group Z′ is identical or differentfrom the group Z; R₈, R₉ and R₁₀, which are identical or different, arechosen from a C₁-C₆ alkyl radical; a monohydroxy(C₁-C₆ alkyl) radical; apolyhydroxy(C₂-C₆ alkyl) radical; a (C₁-C₆)alkoxy(C₁-C₆ alkyl) radical;a cyano(C₁-C₆ alkyl) radical; an aryl radical; a benzyl radical; anamido(C₁-C₆ alkyl) radical; a tri(C₁-C₆)alkylsilane(C₁-C₆ alkyl)radical; and an amino(C₁-C₆ alkyl) radical, wherein the amine isprotected with a radical chosen from (C₁-C₆)alkylcarbonyl, carbamyl, and(C₁-C₆)alkylsulphonyl; two of the radicals R₈, R₉ and R₁₀ may also form,together with the nitrogen atom to which they are attached, a saturated5- or 6-membered ring containing atoms selected from carbon andheteroatoms; one of the radicals R₈, R₉ and R₁₀ may also be chosen froma group Z′, wherein Z′ has the same definition as Z, and wherein thegroup Z′ is identical or different from the group Z; R₁₁ is chosen froma C₁-C₆ alkyl radical; a monohydroxy(C₁-C₆ alkyl) radical; apolyhydroxy(C₂-C₆ alkyl) radical; an aryl radical; a benzyl radical; anamino(C₁-C₆ alkyl) radical; an amino(C₁-C₆ alkyl) radical, wherein theamine is protected with a radical chosen from (C₁-C₆)alkylcarbonyl,carbamyl, and a (C₁-C₆)alkylsulphonyl radical; a carboxy(C₁-C₆ alkyl)radical; a cyano(C₁-C₆ alkyl) radical; a carbamyl(C₁-C₆ alkyl) radical;a trifluoro(C₁-C₆ alkyl) radical; a tri(C₁-C₆)alkylsilane(C₁-C₆ alkyl)radical; a sulphonamido(C₁-C₆ alkyl) radical; a(C₁-C₆)alkylcarboxy(C₁-C₆ alkyl) radical; a (C₁-C₆)alkylsulphinyl(C₁-C₆alkyl) radical; a (C₁-C₆)alkylsulphonyl(C₁-C₆ alkyl) radical; a(C₁-C₆)alkylketo(C₁-C₆ alkyl) radical; an N-(C₁-C₆)alkylcarbamyl(C₁-C₆alkyl) radical; and an N-(C₁-C₆)alkylsulphonamido(C₁-C₆ alkyl) radical;x and y are integers equal to 0 or 1, with the following conditions: inthe unsaturated cationic groups of formula (II): when x is 0, thelinking arm D is attached to the nitrogen atom; when x is 1, the linkingarm D is attached to one of E, G, J or L; y may only be 1: 1) when E, G,J and L are simultaneously a carbon atom, and the radical R₇ is carriedby the nitrogen atom of the unsaturated ring; or 2) when at least one ofE, G, J and L is a nitrogen atom onto which the radical R₇ is attached;in the unsaturated cationic groups of formula (III): when x is 0, thelinking arm D is attached to the nitrogen atom; when x is 1, the linkingarm D is attached to one of E, G, J, L or M; y may only take the value 1when at least one of E, G, J, L and M is a divalent atom, and theradical R₇ is carried by the nitrogen atom of the unsaturated ring; inthe cationic groups of formula (IV): when x is 0, then the linking arm Dis attached to the nitrogen atom carrying the radicals R₈ to R₁₀; when xis 1, then two of the radicals R₈ to R₁₀ conjointly form, with thenitrogen atom to which they are attached, a saturated 5- or 6-memberedring as defined above and the linking arm D is carried by a carbon atomof the saturated ring; X is chosen from monovalent and divalent anions;it being understood that: the number of unsaturated cationic groups Z offormula (II), in which at least one of E, G, J and L is a nitrogen atomis at least equal to
 1. 2. A cationic aminoanthraquinone or anacid-addition salt thereof according to claim 1, wherein D is chosenfrom linear and branched alkyl chains containing from 1 to 14 carbonatoms.
 3. A cationic aminoanthraquinone or an acid-addition salt thereofaccording to claim 1, wherein the at least one heteroatom which mayinterrupt the alkyl chains of the linking arm D is chosen from oxygen,sulphur, and nitrogen.
 4. A cationic aminoanthraquinone or anacid-addition salt thereof according to claim 1, wherein the 5- or6-membered ring formed from two of the radicals R₈, R₉, and R₁₀,together with the nitrogen to which they are attached, is chosen from apyrrolidine ring, a piperidine ring, a piperazine ring, and a morpholinering, and wherein said rings are unsubsituted or substituted with ahalogen atom, a hydroxyl radical, a C₁-C₆ alkyl radical, amonohydroxy(C₁-C₆ alkyl) radical, a polyhydroxy(C₂-C₆ alkyl) radical, anitro radical, a cyano radical, a cyano(C₁-C₆ alkyl) radical, a C₁-C₆alkoxy radical, a tri(C₁-C₆)alkylsilane(C₁-C₆ alkyl) radical, an amidoradical, an aldehydo radical, a carboxyl radical, a keto(C₁-C₆ alkyl)radical, a thio radical, a thio(C₁-C₆ alkyl) radical, a (C₁-C₆)alkylthio radical, an amino radical, and an amino radical protected witha radical chosen from (C₁-C₆)alkylcarbonyl, carbamyl, and(C₁-C₆)alkylsulphonyl.
 5. A cationic aminoanthraquinone or anacid-addition salt thereof according to claim 1, wherein the rings ofthe unsaturated groups Z of formula (II) are chosen from pyrrole,imidazole, pyrazole, oxazole, thiazole and triazole rings.
 6. A cationicaminoanthraquinone or an acid-addition salt thereof according to claim1, wherein the rings of the unsaturated groups Z of formula (III) arechosen from pyridine, pyrimidine, pyrazine, oxazine and triazine rings.7. A cationic aminoanthraquinone or an acid-addition salt thereofaccording to claim 1, wherein in formula (IV), two of the radicals R₈,R₉ and R₁₀ form a ring chosen from pyrrolidine, piperidine, piperazine,and morpholine, wherein said ring is unsubstituted or substituted with asubstituent chosen from a halogen atom, a hydroxyl radical, a C₁-C₆alkyl radical, a monohydroxy(C₁-C₆ alkyl) radical, a polyhydroxy(C₂-C₆alkyl) radical, a nitro radical, a cyano radical, a cyano(C₁-C₆ alkyl)radical, a C₁-C₆ alkoxy radical, a tri(C₁-C₆)alkylsilane(C₁-C₆ alkyl)radical, an amido radical, an aldehydo radical, a carboxyl radical, a(C₁-C₆ alkyl)carbonyl radical, a thio radical, a thio(C₁-C₆ alkyl)radical, a (C₁-C₆)alkylthio radical, an amino radical, and an aminoradical protected with a radical chosen from (C₁-C₆)alkylcarbonyl,carbamyl, and (C₁-C₆)alkylsulphonyl.
 8. A cationic aminoanthraquinone oran acid-addition salt thereof according to claim 1, wherein said X⁻ ischosen from a halogen atom, a hydroxide, a hydrogen sulphate and a(C₁-C₆)alkyl sulphate.
 9. A cationic aminoanthraquinone or anacid-addition salt thereof according to claim 1, wherein said cationicaminoanthraquinone is:1-[2-(9,10-Dioxo-9,10-dihydroanthracen-1-ylamino)ethyl]-3-methyl-3H-imidazol-1-iumbromide,1-Methyl-3-[3-(4-methylamino-9,10-dioxo-9,10-dihydroanthracen-1-ylamino)propyl]-3H-imidazol-1-iumhydrogen sulphate,1-[2-(4-Hydroxy-9,10-dioxo-9,10-dihydroanthracen-1-ylamino)ethyl]-3-methyl-3H-imidazol-1-iumbromide,1-[3-(9,10-Dioxo-9,10-dihydroanthracen-1-ylamino)propyl]-3-methyl-3H-imidazol-1-iummethosulphate,1-[3-(4-Hydroxy-9,10-dioxo-9,10-dihydroanthracen-1-ylamino)propyl]-3-methyl-3H-imidazol-1-iummethosulphate,1-{3-[4-(2-Hydroxyethylamino)-9,10-dioxo-9,10-dihydroanthracen-1-ylamino]propyl}-3-methyl-3H-imidazol-1-iummethosulphate,1-{3-[4-(2,3-Dihydroxypropylamino)-9,10-dioxo-9,10-dihydroanthracen-1-ylamino]propyl}-3-methyl-3H-imidazol-1-iummethosulphate,1,4-bis[3-(9,10-Dioxo-9,10-dihydroanthracen-1,4-diylamino)propyl]-3-methyl-3H-imidazol-1-iumdimethosulphate,1-[2-(9,10-Dioxo-9,10-dihydroanthracen-2-ylamino)ethyl]-3-methyl-3H-imidazol-1-iumbromide,1-[2-(9,10-Dioxo-9,10-dihydroanthracen-2-ylamino)ethyl]-2-methyl-3H-pyrazol-1-iumbromide,1-[2-(9,10-Dioxo-9,10-dihydroanthracen-1-ylamino)ethyl]-2-methyl-3H-pyrazol-1-iumbromide,1,5-bis[3-(9,10-Dioxo-9,10-dihydroanthracen-1,5-diylamino)propyl]-3-methyl-3H-imidazol-1-iumdimethosulphate,1,8-bis[3-(9,10-Dioxo-9,10-dihydroanthracen-1,8-diylamino)propyl]-3-methyl-3H-imidazol-1-iumdimethosulphate,1-[2-(5,8-Diamino-9,10-dioxo-9,10-dihydroanthracen-1-ylamino)ethyl]-3-methyl-3H-imidazol-1-iumbromide, or1-[3-(5,8-Diamino-9,10-dioxo-9,10-dihydroanthracen-1-ylamino)propyl]-3-methyl-3H-imidazol-1-iummethosulphate.
 10. A cationic aminoanthraquinone or an acid-additionsalt thereof according to claim 1, wherein said acid-addition salt ischosen from hydrochlorides, hydrobromides, sulphates, citrates,succinates, tartrates, lactates, and acetates.